Phenoxyalkyl-substituted heteroaromatics and a method for controlling pests

ABSTRACT

Phenoxyalkyl-substituted heteroaromatics of the formulae Ia and Ib ##STR1## where the substituents have the following meanings: R 1  C 1  -C 12  -alkyl, C 2  -C 12  -alkenyl, C 2  -C 12  -alkynyl, C 1  -C 12  -haloalkyl, C 2  -C 12  -haloalkenyl, C 2  -C 12  -haloalkynyl, C 3  -C 12  -alkoxyalkyl, C 3  -C 8  -cycloalkyl, C 4  -C 12  -cycloalkylalkyl, C 3  -C 8  -halocycloalkyl, C 4  -C 12  -halocycloalkylalkyl, C 4  -C 12  -cycloalkylhaloalkyl or C 4  -C 12  -halocycloalkylhaloalkyl; 
     Z hydrogen, halogen, C 1  -C 8  -alkyl, C 1  -C 8  -alkoxy, C 1  -C 4  -haloalkyl, C 1  -C 4  -haloalkoxy, C 3  -C 10  -cycloalkyl, nitro or cyano in the case of Ia and hydrogen, halogen, or C 1  -C 4  -alkyl in the case of Ib; 
     X O, S, SO 2  ; 
     Q a  substituted or unsubstituted azole; 
     Q b  substituted or unsubstituted heteroaromatic; 
     methods of manufacturing compounds Ia and Ib, and their use for combating pests.

The present invention relates to novel phenoxyalkyl-substitutedheteroaromatics of the general formulae Ia and Ib ##STR2## where R¹ isC₁ -C₁₂ -alkyl, C₂ -C₁₂ -alkenyl, C₂ -C₁₂ -alkynyl, C₁ -C₁₂ -haloalkyl,C₂ -C₁₂ -haloalkenyl, C₂ -C₁₂ -haloalkynyl, C₃ -C₁₂ -alkoxyalkyl, C₃ -C₈-cycloalkyl, C₄ -C₁₂ -cycloalkylalkyl, C₃ -C₈ -halocycloalkyl, C₄ -C₁₂-halocycloalkylalkyl, C₄ -C₁₂ -cycloalkylhaloalkyl or C₄ -C₁₂-halocycloalkylhaloalkyl, X is O, S or SO₂, Z is hydrogen, halogen, C₁-C₈ -alkyl, C₁ -C₈ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₃-C₁₀ -cycloalkyl, nitro or cyano in the case of the heteroaromaticQ_(a), and is hydrogen, halogen or C₁ -C₄ -alkyl in the case of theheteroaromatic Q_(b), R² is hydrogen or C₁₋₄ -alkyl, Q_(a) is anunsubstituted or substituted azole radical of the formula IIa-IIf##STR3## where R³ to R¹⁴ are each hydrogen, halogen, C₁ -C₈ -alkyl, C₁-C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₃ -C₁₀ -cycloalkyl or aryl which isunsubstituted or monosubstituted to trisubstituted by halogen, C₁ -C₈-alkoxy, C₁ -C₄ -haloalkyl or C₁ -C₄ -haloalkoxy, and Q_(b) is a5-membered heteroaromatic which is bonded via a carbon atom and isunsubstituted or monosubstituted or polysubstituted by halogen, C₁ -C₈-alkyl, C₂ -C₈ -alkenyl, C₁ -C₄ -haloalkyl, C₁ -C₈ -alkoxy, C₁ -C₈-alkylthio, C₂ -C₈ -alkoxyalkyl or C₃ -C₁₀ -cycloalkyl.

The present invention furthermore relates to pesticides which containthe compounds Ia and Ib as active ingredients, and a method forcontrolling pests.

EP-A-132 606 discloses N-substituted azoles as insecticidal andacaricidal active ingredients. However, the action of these compounds isunsatisfactory.

EP-A No. 0 203 798 describes, for example, 1,3-thiazole which isphenoxyethoxy-substituted in the 2-position, of the structure A ##STR4##Phenoxymethyl-substituted heteroaromatics are disclosed in DE-A No. 2516 331 and EP-A No. 239 047. The insecticidal action of these compoundsis also unsatisfactory.

It is an object of the present invention to provide novelphenoxyalkyl-substituted heteroaromatics Ia and Ib having an improvedaction.

We have found that this object is achieved by the novelphenoxyalkyl-substituted heteroaromatics defined at the outset, andprocesses for their preparation. We have also found that the compoundsIa and Ib are very suitable for controlling pests.

The compounds Ia and Ib are obtainable by the following methods:

For example, a phenol III is reacted with an N-methylazole IVa or with aheteroaromatic IVb having a 5-membered ring, in the presence of a baseat from (-20°) to 250° C., preferably from 20° to 120° C, in accordancewith the following equations: ##STR5##

Some of the phenols III are known from Houben/Weyl, Vol. VI, 3, Methodender organischen Chemie, Thieme Verlag, 1965, page 49 et seq. and 85 etseq., or can be prepared by the methods described there.

Some of the N-methylazoles IVa are disclosed in Heterocycles 24 (1986),2233-2237, or can be prepared by the method described there, inaccordance with the following equation: ##STR6##

The heteroaromatics IVb are either known and are in some casescommercially available or can be prepared by generally known chemicalprocesses. Processes for the preparation of thiophene derivatives aredescribed in, for example, Comprehensive Heterocyclic Chemistry, A. R.Katritzky and C. W. Rees, Vol. 4, page 863 et seq., Pergamon Press,1984; those for the preparation of furan derivatives are described in,for example, DE-A No. 35 14 384, DE-A No. 35 46 371 or Advances inHeterocyclic Chemistry, 30 (1982), page 167 et seq.; those for thepreparation of pyrrole derivatives are described in, for example,Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees,Vol. 4, page 313 et seq., Pergamon Press, 1984; those for thepreparation of thiazole derivatives, oxazole derivatives, isothiazolederivatives, thiadiazole derivatives and oxadiazole derivatives aredescribed in, for example, Comprehensive Heterocyclic Chemistry, A. R.Katritzky and C. W. Rees, Vol. 6, pages 131, 177, 235, 447 and 365 etseq., Pergamon Press, 1984; those for the preparation of imidazolederivatives are described in, for example, Advances in HeterocyclicChemistry, 27 (1980), 242 et seq.; those for the preparation of pyrazolederivatives are described in, for example, Heteroaromatic NitrogenCompounds, The Azoles, page 31 et seq., Cambridge University Press,1976; those for the preparation of triazole derivatives are describedin, for example, Comprehensive Heterocyclic Chemistry, A. R. Katritzkyand C. W. Rees, Vol. 5, page 669 et seq., Pergamon Press, 1984, andthose for the preparation of isoxazole derivatives are described in, forexample, DE-A No. 25 49 962 and DE-A No. 27 54 832.

Usually, not less than an equivalent amount of a base is added to IIIand/or IVa or IVb, but the base may also be used in excess or, ifnecessary also as a solvent.

Examples of suitable bases are hydroxides of alkali metals and alkalineearth metals, such as sodium hydroxide, potassium hydroxide and calciumhydroxide, alcoholates of alkali metals and alkaline earth metals, suchas sodium methylate, sodium ethylate, calcium methanolate or potassiumtert-butylate, alkali metal or alkaline earth metal hydrides, such assodium hydride, potassium hydride or calcium hydride, alkali metal oralkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate or calcium carbonate, aliphatic amines, such as dimethylamine,triethylamine or diisopropylamine, heterocyclic amines, such aspiperidine, piperazine or pyrrolidine, aromatic amines, such as pyridineor pyrrole, and, if desired, also alkyllithium compounds, such asn-butyllithium.

The reaction is advantageousely carried out in a solvent or diluent.Examples of suitable solvents or diluents are aliphatic hydrocarbons,such as n-pentane, n-hexane, the hexane isomer mixture and petroleumeither, aromatic hydrocarbons, such as benzene, toluene, the xylenes andtheir isomer mixtures, and gasoline, alcohols, such as methanol,ethanol, n-propanol and isopropanol, ethers, such as diethyl ether,di-n-butyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane,ketones, such as acetone, methyl ethyl ketone and methyl isopropylketone, nitriles, such as acetonitrile and propionitrile, and aproticdipolar solvents, such as dimethylformamide, dimethyl sulfoxide orpyridine. Mixtures of these substances can also be used as solvents anddiluents.

Instead of the phenol III plus the base, it is also possible to reactthe phenolate anion of III directly with IVa or IVb. In this case, thereaction temperatures are from -20° to 120° C., preferably from -20° to80° C.

The anions of the phenols III are known in the form of their metalsalts, such as sodium or potassium salt, or can be generated in situfrom phenols III by reaction with conventional metallization reagentsdescribed in, for example, Houben/Weyl (see above), such as sodiummethylate, sodium ethylate, potassium tert-butylate, sodium hydride,potassium hydride or n-butyl-lithium.

The reaction is advantageously carried out in a solvent or diluent.Examples of suitable solvents or diluents are aliphatic hydrocarbons,such as n-pentane, n-hexane, the hexane isomer mixture and petroleumether, halohydrocarbons, such as chlorobenzene, methylene chloride,ethylene chloride, chloroform and tetrachloroethylene, aromatichydrocarbons, such as benzene, toluene, the xylenes and their isomermixtures and gasoline, ethers, such as diethyl ether, di-n-butyl ether,methyl tert-butyl ether, tetrahydrofuran and dioxane, ketones, such asacetone, methyl ethyl ketone and methyl isopropyl ketone, and aproticdipolar solvents, such as dimethylformamide, dimethyl sulfoxide orpyridine. Mixtures of these substances may also be used as solvents anddiluents.

In every case, Y is a conventional leaving group, for example a sulfonicacid radical or a halogen. Among the sulfonic acid radicals,methanesulfonyl, trifluoromethanesulfonly and p-toluenesulfonyl arepreferred, where preferred halogens are chlorine and bromine, chlorinebeing particularly preferred.

For the preparation of the novel compounds Ia and Ib by the methodsdescribed above, starting materials are usually employed in astoichiometric ratio. An excess of one or other of the startingmaterials may be quite advantageous in some specific cases.

The reactions usually take place at a sufficient rate at above -20° C.In general, 120° C. need not be exceeded. Since in some cases thereactions take place with evolution of heat, it may be advantageous toprovide a means of cooling.

The reaction mixtures are worked up in a conventional manner, forexample by adding water, separating the phases and carrying out columnchromatography. Some of the novel compounds of the formulae Ia and Ibare obtained in the form of colorless or pale brown, viscous oils, whichcan be freed from the final volatile constitutents by prolonged heatingto moderately elevated temperatures under reduced pressure (incipientdistillation) and can be purified in this manner. If the compounds ofthe formulae Ia and Ib are obtained in crystalline form, they can bepurified by recrystallization.

The substituents in formula I have the following specific meanings:

R¹ is straight-chain or branched C₁ -C₁₂ -alkyl, preferably C₁ -C₈-alkyl, particularly preferably branched C₃ -C₈ -alkyl, such asisopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 1-methylbutyl,isohexyl, 1-methylpentyl, isoheptyl, 1-methylhexyl, 1-methylheptyl,1,3-dimethylbutyl, 1,2-dimethylbutyl, 3-methylpentyl, 4-methylbutyl,1-ethylpropyl or 1-ethylbutyl;

straight-chain or branched C₂ -C₁₂ -alkenyl, preferably C₂ -C₈ -alkenyl,particularly preferably C₃ -C₆ -alkenyl, such as allyl, 1-methylallyl,1,3-dimethylbut-2-enyl, 1-methylbut-2-enyl or but-3-en-1-yl;

straight-chain or branched C₂ -C₁₂ -alkynyl, preferably C₂ -C₈ -alkynyl,particularly preferably C₂ -C₄ -alkynyl, such as ethynyl, propynyl,prop-2-ynyl, 1-methylprop-2-ynyl, but-2-ynyl or but-3-ynyl;

straight-chain or branched C₁ -C₁₂ -haloalkyl, preferably C₁ -C₄-haloalkyl, particularly preferably C₁ -C₄ -fluoro- or chloroalkyl, suchas trifluoromethyl, difluoromethyl, fluoromethyl, trichloromethyl,pentfluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl,1-fluoromethyl-2-fluoroethyl or 1-chloromethyl-2-chloroethyl;

straight-chain or branched C₂ -C₁₂ -haloalkenyl, preferably C₂ -C₄-haloalkenyl, particularly preferably C₂ -C₄ -fluoro- or chloroalkenyl,such as 1,2,2-trifluoroethenyl, 1,2,2-trichloroethenyl,3,3-difluoroprop-2-enyl or 3,3-dichloroprop-2-enyl;

straight-chain or branched C₃ -C₁₂ -alkoxyalkyl, preferably C₃ -C₉-alkoxyalkyl, particularly preferably C₁ -C₄ -alkoxysubstituted C₁ -C₅-alkoxyalkyl, for example 2-methoxyethyl, 2-methoxypropyl,3-methoxyprop-2-yl, 3-methoxybutyl, 4-methoxybut-2-yl, 4-methoxybut-3yl,5-methoxypent-3-yl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl,3-ethoxybutyl, 3-ethoxybut-2-yl, 5-ethoxypent-2-yl, 2-propoxyethyl,2-propoxypropyl, 3-propoxybutyl, butoxymethyl or 2-butoxyprop-2-yl;

C₃ -C₈ -cycloalkyl, preferably C₃ -C₆ -cycloalkyl, such as cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl; C₄ -C₁₂ -cycloalkylalkyl,preferably C₄ -C₈ -cycloalkylalkyl, such as cyclopropylmethyl,cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethylor cyclohexylethyl;

C₃ -C₈ -halocycloalkyl, preferably C₃ -C₆ -halocycloalkyl, particularlypreferably C₃ -C₆ -fluoro- or chlorocycloalkyl, such as2,2-difluorocyclopropyl or 2,2-dichlorocyclopropyl;

C₄ -C₁₂ -halocycloalkylalkyl, preferably C₄ -C₈ -halocycloalkylalkyl,particularly preferably C₄ -C₈ -fluoro- or chlorocycloalkylalkyl, suchas 2,2-difluorocycloprop-1-ylmethyl or 2,2-dichlorocycloprop-1-ylmethyl;

C₄ -C₁₂ -cycloalkylhaloalkyl, preferably C₄ -C₈ -cycloalkylhaloalkyl,particularly preferably C₄ -C₈ -cycloalkylfluoro- or -chloroalkyl, suchas 2-cyclopropyl-2-chloroethyl or 2-cyclopropyl-1,1-difluoroethyl, or

C₄ -C₁₂ -halocycloalkylhaloalkyl, preferably C₄ -C₈-halocycloalkylhaloalkyl, particularly preferably C₄ -C₈ -fluoro- orchlorocycloalkylfluoro- or chloroalkyl, such as2,2-dichlorocycloprop-1-yl-2-chloroethyl.

X is O, S or SO₂, preferably O or S, particularly preferably O.

In the case of Q_(a), Z is hydrogen;

halogen, preferably fluorine or chlorine;

straight-chain or branched C₁ -C₈ -alkyl, preferably straight-chain orbranched C₁ -C₄ -alkyl, such as methyl, ethyl, propyl, isopropyl, butylor isobutyl, particularly preferably C₁ - or C₂ -alkyl, such as methylor ethyl; straight-chain or branched C₁ -C₈ -alkoxy, preferablystraight-chain or branched C₁ -C₄ -alkoxy, such as methoxy, ethoxy,propoxy, isopropoxy or butoxy, particularly preferably C₁ - or C₂-alkoxy, such as methoxy or ethoxy; straight-chain or branched C₁ -C₄-haloalkyl, preferably C₁ - or C₂ -fluoro or chloroalkyl, particularlypreferably trifluoromethyl or trichloromethyl;

straight-chain or branched C₁ -C₄ -haloalkoxy, preferably C₁ - or C₂-fluoro- or chloroalkoxy, particularly preferably trifluoromethoxy ortrichloromethoxy;

C₃ -C₁₀ -cycloalkyl, preferably C₃ -C₆ -cycloalkyl, such as cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl, particularly preferablycyclopropyl;

nitro or

cyano;

in the case of Q_(b), Z is hydrogen or halogen, preferably fluorine,chlorine or bromine, particularly preferably fluorine or chlorine, C₁-C₄ -alkyl, such as methyl, ethyl, propyl, isopropyl or butyl,particularly preferably methyl or ethyl.

R² is preferably hydrogen or C₁ -C₄ -alkyl, such as methyl, ethyl,propyl, isopropyl or butyl, particularly preferably methyl.

R³ -R¹⁴ independently of one another are each hydrogen;

halogen, preferably fluorine or chlorine;

straight-chain or branched C₁ -C₈ -alkyl, preferably straight-chain orbranched C₁ -C₄ -alkyl, such as methyl, ethyl, propyl, isopropyl, butylor isobutyl, particularly preferably C₁ - or C₂ -alkyl, such as methylor ethyl;

straight-chain or branched C₁ -C₄ -haloalkyl, preferably C₁ -C₂ -fluoro-or chloroalkyl, particularly preferably trifluoromethyl ortrichloromethyl;

straight-chain or branched C₁ -C₈ -alkoxy, preferably straight-chain orbranched C₁ -C₄ -alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy orbutoxy, particularly preferably C₁ - or C₂ -alkoxy, such as methoxy orethoxy; C₃ -C₁₀ -cycloalkyl, preferably C₃ -C₆ -cycloalkyl, such ascyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, particularlypreferably cyclopropyl;

aryl, preferably phenyl, 1-naphthyl or 2-naphthyl, particularlypreferably phenyl,

aryl which is monosubstituted to trisubstituted by halogen, preferablyphenyl which is monosubstituted by fluorine or chlorine, such as2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl,3-chlorophenyl or 4-chlorophenyl;

aryl which is monosubstituted to trisubstituted by straight-chain orbranched C₁ -C₈ -alkyl, preferably phenyl which is monosubstituted bystraight-chain or branched C₁ -C₄ -alkyl, particularly preferably phenylwhich is monosubstituted by C₁ - or C₂ -alkyl, such as 4-methylphenyl or4-ethylphenyl;

phenyl which is monosubstituted to trisubstituted by straight-chain orbranched C₁ -C₈ -alkoxy, particularly preferably phenyl which ismonosubstituted by C₁ - or C₂ -alkoxy, such as 4-methoxyphenyl or4-ethoxyphenyl;

aryl which is monosubstituted to trisubstituted by straight-chain orbranched C₁ -C₄ -haloalkyl, preferably phenyl which is monosubstitutedby C₁ - or C₂ -fluoro- or chloroalkyl, particularly preferably phenylwhich is monosubstituted by trifluoromethyl or trichloromethyl, such as4-trifluoromethylphenyl or 4-trichloromethylphenyl;

aryl which is monosubstituted to trisubstituted by straight-chain orbranched C₁ -C₄ -haloalkoxy, preferably phenyl which is monosubstitutedby C₁ - or C₂ -fluoro- or chloroalkoxy, particularly preferably phenylwhich is monosubstituted by trifluoromethyl or trichloromethoxy, such as4-trifluoromethoxyphenyl or 4-trichloromethoxyphenyl, and

Q_(b) is an unsubstituted or substituted heteroaromatic having a5-membered ring and from 1 to 4, in particular 1 or 2, heteroatoms, suchas nitrogen, sulfur or oxygen, preferably thiophen-2-yl, thiophen-3-yl,thiazol-5-yl, thiazol-4-yl, thiazol-2-yl, oxazol-5-yl, oxazol-4-yl,oxazol-2-yl, imidazol-5-yl, imidazol-4-yl, imidazol-2-yl,isothiazol-5-yl, isothiazol-3-yl, pyrazol-3-yl, pyrazol-4-yl,pyrazol-5-yl, isoxazol-5-yl, isoxazol-3-yl, 1,3,4-thiadiazol-2-yl,1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-3-yl, 1,3,4-triazol-2-yl or1,2,4-thiadiazol-3-yl, particularly preferably thiophen-2-yl,thiophen-3-yl, thiazol-4-yl, imidazol-5-yl, pyrazol-3-yl,1,3,4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-3-yl,isoxazol-5-yl or isoxazol-3-yl.

The hetaryl radical having a five-membered ring may be unsubstituted ormonosubstituted or polysubstituted by:

halogen, preferably fluorine, chlorine or bromine, particularlypreferably chlorine or bromine, C₁ -C₈ -alkyl, preferably C₁ -C₄ -alkyl,particularly preferably methyl, ethyl, isopropyl or tert-butyl, C₂ -C₈-alkenyl, preferably C₂ -C₄ -alkenyl, particularly preferably ethenyl,1-methylethenyl, propenyl or 2-methylpropenyl,

C₁ -C₄ -haloalkyl, preferably C₁ - or C₂ -haloalkyl which is substitutedby fluorine or chlorine, particularly preferably trifluoromethyl or2,2,2-trifluoroeth-1-yl,

C₁ -C₈ -alkoxy, preferably C₁ -C₃ -alkoxy, particularly preferablymethoxy, ethoxy, n-propoxy or isopropoxy,

C₁ -C₈ -alkylthio, preferably C₁ -C₃ -alkylthio, particularly preferablymethylthio, ethylthio, n-propylthio or isopropylthio,

C₂ -C₈ -alkoxyalkyl, preferably C₂ -C₄ -alkoxyalkyl, particularlypreferably methoxymethyl, 1-methoxyethyl, 2-methoxyethyl or1-methoxypropyl, or

C₃ -C₈ -cycloalkyl, preferably C₃ -C₅ -cycloalkyl, such as cyclopropyl,cyclobutyl or cyclopentyl.

The novel compounds Ia and Ib may contain one or more centers ofasymmetry in the substituent R¹. The present invention embraces allpossible stereoisomers, such as diastereomers, enantiomers, diastereomermixtures and enantiomer mixtures. The compounds relating to the examplecompounds in the Table are the racemic mixture in each case.

The phenoxyalkyl-substituted aromatics of the formula Ia and Ib aresuitable for effectively combating pests from the class of insects,mites and nematodes. They may be used as pesticides in crop protection,and in the hygiene, stores protection and veterinary sectors.

Examples of injurious insects from the Lepidoptera order are Plutellamaculipennis, Leucoptera coffeella, Hyponomeuta malinellus, Argyresthiaconjugella, Sitotroga cerealella, Phthorimaea operculella, Capuareticulana, Sparganothis pilleriana, Cacoecia murinana, Tortrixviridana, Clysia ambiguella, Evetria buoliana, Polychrosis botrana,Cydia pomonella, Laspeyresia molesta, Laspeyresia funebra, Ostrinianubilalis, Loxostege sticticalis, Ephestia kuehniella, Chilosuppressalis, Galleria mellonella, Malacosoma neustria, Dendrolimuspini, Thaumatopoea pityocampa, Phalera bucephela, Cheimatobia brumata,Hibernia defoliaria, Bupalus pinarius, Hyphantria cunea, Agrotissegetum, Agrotis ypsilon, Barathra brassicae, Cirphis unipuncta,Prodenia litura, Laphygma exigua, Panolis flammea, Earis insulana,Plusia gamma, Alabama argillacea, Lymantria dispar, Lymantria monacha,Pieris brassicae, and Aporia crataegi;

examples from the Coleoptera order are Blitophaga undata, Melanotuscommunis, Limonius californicus, Agriotes lineatus, Agriotes obscurus,Agrilus sinuatus, Meligethes aeneus, Atomaria linearis, Epilanchnavaricestris, Phyllopertha horticola, Popillia japonica, Melolonthamelolontha, Melolontha hippocastani, Amphimallus solstitialis, Criocerisasparagi, Lema melanopus, Leptinotarsa decemlineata, Phaedoncochleariae, Phyllotreta nemorum, Chaetocnema tibialis, Phylloideschrysocephala, Diabrotica 12-punctata, Cassida nebulosa, Bruchus lentis,Bruchus rufimanus, Bruchus pisorum, Sitona lineatus, Otiorrhynchussulcatus, Otiorrhynchus ovatus, Hylobies abietis, Byctiscus betulae,Anthonomus pomorum, Anthonomus grandis, Ceuthorrhynchus assimilis,Ceuthorrhynchus napi, Sitophilus granaria, Anisandrus dispar, Ipstypographusand Blastophagus piniperda;

examples from the Diptera order are Lycoria pectorais, Mayetioladestructor, Dasyneura brassicae, Contarinia tritici, Haplodiplosisequestris, Tipula paludosa, Tipula oleracea, Dacus cucurbitae, Dacusoleae, Ceratitis capitata, Rhagoletis cerasi, Rhagoletis pomonella,Anastrepha ludens, Oscinella frit, Phorbia coarctata, Phorbia antiqua,Phorbia brassicae, Pegomya hyoscyami, Anopheles maculipennis, Culexpipiens, Aedes aegypti, Aedes vexans, Tabanus bovinus, Tipula paludosa,Musca domestica, Fannia canicularis, Muscina stabulans, Glossinamorsitans, Oestrus ovis, Chyrysomya macellaria, Chrysomya hominivorax,Lucilia cuprina, Lucilia sericata, and Hypoderma lineata;

examples from the Hymenoptera order are Athalia rosae, Hoplocampaminuta, Monomorium pharaonis, Solenopsis geminata, and Atta sexdens;

examples from the Heteroptera order are Nezara viridula, Eurygasterintegriceps, Blissus leucopterus, Dysdercus cingulatus, Dysdercusintermedius, Piesma quadrata, and Lygus pratensis;

examples from the Homoptera order are Perkinsiella saccharicida,Nilaparvata lugens, Empoasca fabae, Psylla mali, Psylla piri,Trialeurodes vaporariorum, Aphis fabae, Aphis pomi, Aphis sambuci,Aphidula nasturtii, Cerosipha gossypii, Sappaphis mali, Sappaphis mala,Dysaphis radicola, Brachycaudus cardui, Brevicoryne brassicae, Phorodonhumuli, Rhopalomyzus ascalonicus, Myzodes persicae, Myzus cerasi,Dysaulacorthum pseudosolani, Acyrthosiphon onobrychis, Macrosiphonrosae, Megoura viciae, Schizoneura lanuginosa, Pemphigus bursarius,Dreyfusia nordmannianae, Dreyfusia piceae, Adelges laricis, and Viteusvitifolii;

examples from the Isoptera order are Reticulitermes lucifugus,Calotermes flavicollis, Leucotermes flavipes, and Termes natalensis;

examples from the Orthoptera order are Forficula auricularia, Achetadomestica, Gryllotalpa gryllotalpa, Tachycines asynamorus, Locustamigratoria, Stauronotus maroccanus, Schistocerca peregrina, Nomadacrisseptemfasciata, Melanoplus spretus, Melanoplus femur-rubrum, Blattaorientalis, Blattella germanica, Periplaneta americana, and Blaberagigantea.

Examples of mites and ticks (Acarina) belonging to the Arachnida classare Tetranychus telarius, Tetranychus pacificus, Paratetranychuspilosus, Bryobia praetiosa, Ixodes ricinus, Ornithodorus moubata,Amblyomma americanum, Dermacentor silvarum, and Boophilus microplus.

Examples from the Nemathelminthes class are root-knot nematodes, e.g.,Meloidogyne incognita, Meloidogyne hapla, and Meloidogyne javanica,cyst-forming nematodes, e.g., Heterodera rostochiensis, Heteroderaschachtii, Heterodera avenae, Heterodera glycines, and Heteroderatrifolii, and stem and leaf eelworms, e.g., Ditylenchus dipsaci,Ditylenchus destructor, Pratylenchus neglectus, Pratylenchus penetrans,Pratylenchus goodeyi, Pratylenchus curvitatus and Tylenchorhynchusdubius, Tylenchorhynchus claytoni, Rotylenchus robustus,Heliocotylenchus multicinctus, Radopholus similis, Belonolaimuslongicaudatus, Longidorus elongatus, and Trichodorus primitivus.

The active ingredients may be applied for instance as such, or in theform of formulations or application forms prepared therefrom, e.g.,directly sprayable solutions, powders, suspensions, dispersions,emulsions, oil dispersions, pastes, dusts, broadcasting agents, orgranules by spraying, atomizing, dusting, broadcasting or watering. Theforms of application depend entirely on the purpose for which the agentsare being used, but they must ensure as fine a distribution of theactive ingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersionsto be sprayed direct, mineral oil fractions of medium to high boilingpoint, such as kerosene or diesel oil, further coal-tar oils, and oilsof vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons such as benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives suchas methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions or wettable powders by adding water. To prepareemulsions, pastes and oil dispersions the ingredients as such ordissolved in an oil or solvent may be homogenized in water by means ofwetting or dispersing agents, adherents or emulsifiers. Concentrateswhich are suitable for dilution with water may be prepared from activeingredient, wetting agent, adherent, emulsifying or dispersing agent andpossibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkylsulfonates, alkali metal and alkaline earth metal salts ofdibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcoholsulfates, alkali metal and alkaline earth metal salts of fatty acids,salts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof sulfated fatty alcohol glycol ethers, condensation products ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensation products of naphthalene or naphthalenesulfonic acids withphenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acid, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain flours, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The formulations generally contain from 0.1 to 95, and preferably 0.5 to90% by weight of active ingredient.

Examples of formulations are given below.

I. 5 parts by weight of compound no. A1 is intimately mixed with 95parts by weight of particulate kaolin. A dust is obtained containing 5%by weight of the active ingredient.

II. 30 parts by weight of compound no. A4 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

III. 10 parts by weight of compound no. A50 is dissolved in a mixtureconsisting of 90 parts by weight of xylene, 6 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 2 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 2 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil.

IV. 20 parts by weight of compound no. B1 is dissolved in a mixtureconsisting of 60 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxideand 1 mole of isooctylphenol, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil.

V. 80 parts by weight of compound no. B10 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid,10 parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 7 parts by weight of powdered silicagel, and triturated in a hammer mill.

The active ingredient concentrations in the finished formulations mayvary over a wide range. Generally, they are from 0.0001 to 10, andpreferably from 0.01 to 1, %. The active ingredients may alsosuccessfully be used in the ultra-low-volume (ULV) method, where it ispossible to apply formulations containing more than 95 wt % of activeingredient, or even the active ingredient without additives.

In the open, the amount of active ingredient applied is for example from0.001 to 2, particularly from 0.01 to 1, kg/ha.

There may be added to the active ingredients (if desired, immediatelybefore use (tankmix)) oils of various types, herbicides, fungicides,other pesticides and bactericides. These agents may be added to theactive ingredients according to the invention in a weight ratio of from1:10 to 10:1.

MANUFACTURING EXAMPLES (A) N-Phenoxymethyl-substituted azoles (Q_(a))1-[4-(1-Methyl-1-propyloxy)-phenoxymethyl]-4,5-dichloroimidazole(Compound no. A4)

Under a nitrogen blanket and at room temperature (about 20° C.), 5.0 gof 4-(1-methyl-1-propyloxy)-phenol in 20 ml of anhydrousdimethylformamide is dripped into 0.79 g of 80% strength sodium hydridein 50 ml of anhydrous dimethylformamide. After the exothermic reactionhas subsided (evolution of hydrogen), the mixture is stirred for afurther 30 minutes at 60° C. Subsequently, 6.12 g of1-chloromethyl-4,5-dichloroimidazole in 20 ml of anhydrousdimethylformamide is dripped in at room temperature. The whole is pouredinto 150 ml of ice water, followed by extraction three times with ethylacetate. The organic phases are washed with 5% strength sodium hydroxidesolution and with water. Drying over sodium sulfate and concentrationunder reduced pressure gives a crude product which is purified bychromatography on silica gel using toluene/ethyl acetate (9:1) aseluant. There is obtained 4.3 g of1-[4-(1-methyl-1-propyloxy)-phenoxymethyl]-4,5-dichloroimidazole; n_(D)²² =1.5475.

1-[4-(3,3-Dimethyl-1-propyloxy)-phenoxymethyl]-4,5-dichloroimidazole(Compound no. A50)

Under a nitrogen blanket and at room temperature, 5.8 g of4-(3,3-dimethyl-1-proplyoxy)-phenol in 20 ml of anhydrousdimethylformamide is dripped into 0.79 g of 80% strength sodium hydridein 50 ml of anhydrous dimethylformamide. After hydrogen evolution hassubsided, the mixture is stirred for a further hour at 60° C.Subsequently, 6.12 g of 1-chloromethyl-4,5-dichloroimidazole in 20 ml ofanhydrous dimethylformamide is dripped in at room temperature. The wholeis then stirred for 3 hours at 80° C. and overnight at room temperature.The mixture is then poured into 100 ml of ice water, followed byextraction three times with methyl tert-butyl ether. The organic phasesare washed with 5% strength sodium hydroxide solution and three timeswith water, dried over sodium sulfate and concentrated under reducedpressure. The residue is recrystallized from cyclohexane. There isobtained 7.4 g of1-[4-(3,3-dimethyl-1-propyloxy)-phenoxymethyl]-4,5-dichloroimidazolehaving a melting point of 105°-108° C.

Compounds Iaa to Iaf listed in Tables 1 to 6 below may be obtained inaccordance with these directions.

Compounds Iaa to Iaf without any physical data in Tables 1 to 6 may bereadily obtained from appropriate starting materials; they are expectedto have a similar action.

                  TABLE 1                                                         ______________________________________                                         ##STR7##                     (Iaa)                                                                           R.sup.4 =  Phys.                              No.  R.sup.1         Z      R.sup.3                                                                           R.sup.5                                                                             X    data                               ______________________________________                                        A1   (CH.sub.3).sub.2 CH                                                                           H      H   Cl    O    n.sub.D.sup.24 :                                                              1.5421                             A2   (CH.sub.3).sub.2 CH                                                                           H      H   Cl    S                                       A3   (CH.sub.3).sub.2 CH                                                                           H      H   Cl    SO.sub.2                                A4                                                                                  ##STR8##       H      H   Cl    O    n.sub.D.sup.23 : 1.5475            A5                                                                                  ##STR9##       H      H   Cl    S    n.sub.D.sup.24 : 1.5795            A6                                                                                  ##STR10##      H      H   Cl    SO.sub.2                                                                           mp: 111- 114° C.            A7                                                                                  ##STR11##      3-F    H   Cl    O                                       A8                                                                                  ##STR12##      3-F    H   Cl    S                                       A9                                                                                  ##STR13##      3-F    H   Cl    SO.sub.2                                A10                                                                                 ##STR14##      3-Cl   H   Cl    O                                       A11                                                                                 ##STR15##      3-Cl   H   Cl    S                                       A12                                                                                 ##STR16##      H      H   Cl    O                                       A13                                                                                 ##STR17##      H      H   Cl    S                                       A14                                                                                 ##STR18##      H      H   Cl    O                                       A15                                                                                 ##STR19##      H      H   Cl    S                                       A16                                                                                 ##STR20##      H      H   Cl    O                                       A17                                                                                 ##STR21##      H      H   Cl    S                                       A18                                                                                 ##STR22##      H      H   Cl    O                                       A19                                                                                 ##STR23##      H      H   Cl    S                                       A20                                                                                 ##STR24##      H      H   Cl    O    n.sub.D.sup.23 : 1.5373            A21                                                                                 ##STR25##      H      H   Cl    S                                       A22                                                                                 ##STR26##      H      H   Cl    O                                       A23                                                                                 ##STR27##      H      H   Cl    S                                       A24                                                                                 ##STR28##      H      H   Cl    O                                       A25                                                                                 ##STR29##      H      H   Cl    S                                       A26                                                                                 ##STR30##      H      H   Cl    SO.sub.2                                A27  CH.sub.2CHCH.sub.2                                                                            H      H   Cl    O                                       A28  CH.sub.2CHCH.sub.2                                                                            H      H   Cl    S                                       A29                                                                                 ##STR31##      H      H   Cl    O                                       A30                                                                                 ##STR32##      H      H   Cl    S                                       A31                                                                                 ##STR33##      H      H   Cl    O                                       A32                                                                                 ##STR34##      H      H   Cl    S                                       A33  Cyclobutyl      H      H   Cl    O                                       A34  Cyclobutyl      H      H   Cl    S                                       A34  Cyclopentyl     H      H   Cl    O                                       A35  cyclopentyl     H      H   Cl    S                                       A36  cyclohexyl      H      H   Cl    O                                       A37  cyclohexyl      H      H   Cl    S                                       A38  cyclopropyl-methyl                                                                            H      H   Cl    O                                       A39  cyclohexyl-methyl                                                                             H      H   Cl    O                                       A40                                                                                 ##STR35##      H      H   Cl    O    mp.: 94- 96° C.             A41                                                                                 ##STR36##      H      H   Cl    S                                       A42                                                                                 ##STR37##      H      H   Cl    SO.sub.2                                A43                                                                                 ##STR38##      3-F    H   Cl    O                                       A44  HCCCH.sub.2     H      H   Cl    O                                       A45  ClCCCH.sub.2    H      H   Cl    O                                       A46                                                                                 ##STR39##      H      H   Cl    O                                       A47                                                                                 ##STR40##      H      H   Cl    O                                       A48  (CH.sub.3).sub.2 CHCH.sub.2                                                                   H      H   Cl    O    mp.:                                                                          65-                                                                           68° C.                      A49  (CH.sub.3).sub.2 CH(CH.sub.2).sub.2                                                           H      H   Cl    O                                       A50  (CH.sub.3).sub.2 CHCH.sub.2                                                                   H      H   Cl    S                                       A51  (C.sub.2 H.sub.5).sub.2 CH                                                                    H      H   Cl    O    n.sub.D.sup.22 :                                                              1.5475                             A52  (CH.sub.2 F).sub.2 CH                                                                         H      H   Cl    O                                       A53  CF.sub.3 CH.sub.2                                                                             H      H   Cl    O                                       A54                                                                                 ##STR41##      H      H   Cl    O                                       A55  ClCHCHCH.sub.2  H      H   Cl    O                                       A56  (CH.sub.3).sub.3 CCH.sub.2                                                                    H      H   Cl    O    mp.:                                                                          105-                                                                          108° C.                     A57  CH.sub.3 CH.sub.2 CH.sub.2                                                                    H      H   Cl    O                                       A58  CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2                                                           H      H   Cl    O                                       A59  CH.sub.3        H      H   Cl    O                                       A60  CH.sub.3 CH.sub.2                                                                             H      H   Cl    O                                       A61  CH.sub.3 (CH.sub.2).sub.2 CH.sub.2                                                            H      H   Cl    S                                       A62  (CH.sub.3).sub.3 C(CH.sub.2).sub.2                                                            H      H   Cl    O                                       A63                                                                                 ##STR42##      H      H   Cl    O                                       A64                                                                                 ##STR43##      H      H   Cl    O                                       A65                                                                                 ##STR44##      H      H   Cl    O    n.sub.D.sup.22 : 1.5365            A66                                                                                 ##STR45##      H      H   Cl    O    n.sub.D.sup.22 : 1.5421            A67                                                                                 ##STR46##      H      H   Cl    O                                       A68                                                                                 ##STR47##      H      H   Cl    O                                       A69                                                                                 ##STR48##      H      H   Cl    O                                       A70                                                                                 ##STR49##      H      H   Cl    O                                       A71                                                                                 ##STR50##      H      H   Cl    O                                       A72                                                                                 ##STR51##      H      H   Cl    O                                       A73                                                                                 ##STR52##      H      H   Cl    O                                       A74                                                                                 ##STR53##      H      H   Cl    O    n.sub.D.sup.22 : 1.5500            A75  CH.sub.3 CH.sub.2 O(CH.sub.2).sub.2                                                           H      H   Cl    O    n.sub.D.sup.22 :                                                              1.5500                             A76                                                                                 ##STR54##      H      H   Cl    O                                       A77  CH.sub.3 O(CH.sub.2).sub.2                                                                    H      H   Cl    O    n.sub.D.sup.22 :                                                              1.5575                             A78                                                                                 ##STR55##      H      H   Cl    S                                       A79                                                                                 ##STR56##      H      H   H     O                                       A80                                                                                 ##STR57##      H      H   H     S                                       A81                                                                                 ##STR58##      H      H   H     SO.sub.2                                A82  (CH.sub.3).sub.2 CH                                                                           H      H   H     O                                       A83                                                                                 ##STR59##      H      H   H     O                                       A84  CH.sub.3 O(CH.sub.2).sub.2                                                                    H      H   H     O                                       A85                                                                                 ##STR60##      H      H   H     O                                       A86                                                                                 ##STR61##      H      H   H     O                                       A87                                                                                 ##STR62##      H      H   CH.sub. 3                                                                           O                                       A88                                                                                 ##STR63##      H      H   CH.sub.3                                                                            O                                       A89  CH.sub.3 O(CH.sub.2).sub.2                                                                    H      H   CH.sub.3                                                                            O                                       A90  (CH.sub.3).sub.2 CH                                                                           H      H   CH.sub.3                                                                            O                                       A91                                                                                 ##STR64##      H      H   CH.sub.3                                                                            O                                       A92                                                                                 ##STR65##      H      H   CH.sub.3                                                                            O                                       A93                                                                                 ##STR66##      H      H   CH.sub.3                                                                            S                                       A94                                                                                 ##STR67##      H      H   CH.sub.3                                                                            SO.sub.2                                ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                         ##STR68##                    (Iab)                                           No.  R.sup.1       Z     R.sup.6                                                                           R.sup.7                                                                           R.sup.8                                                                           X     Phys. data                         ______________________________________                                        A95  (CH.sub.3).sub.2 CH                                                                         H     H   H   H   O                                        A96  (CH.sub.3).sub.2 CH                                                                         H     H   H   H   S                                        A97                                                                                 ##STR69##    H     H   H   H   O                                        A98                                                                                 ##STR70##    H     H   H   H   S                                        A99                                                                                 ##STR71##    H     H   H   H   SO.sub.2                                 A100 CH.sub.3 OCH.sub.2 CH.sub.2                                                                 H     H   H   H   O                                        A101 CH.sub.3 OCH.sub.2 CH.sub.2                                                                 H     H   H   H   S                                        A102                                                                                ##STR72##    H     H   H   H   O                                        A103                                                                                ##STR73##    H     H   H   H   S                                        A104                                                                                ##STR74##    H     H   H   H   O                                        A105                                                                                ##STR75##    H     H   H   H   S                                        A106                                                                                ##STR76##    H     H   H   H   O                                        A107                                                                                ##STR77##    H     H   H   H   S                                        A108                                                                                ##STR78##    H     H   H   H   SO.sub.2                                 ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                         ##STR79##                    (Iac)                                           No.  R.sup.1        Z     R.sup.9 = R.sup.10                                                                   X    Phys. data                              ______________________________________                                        A109                                                                                ##STR80##     H     H      O    n.sub.D.sup.21 : 1.5310                 A110                                                                                ##STR81##     H     H      S    n.sub.D.sup.21 : 1.5665                 A111                                                                                ##STR82##     H     H      SO.sub.2                                     A112                                                                                ##STR83##     H     H      O    n.sub.D.sup.21 : 1.5635                 A113                                                                                ##STR84##     H     H      S                                            A114 (CH.sub.3).sub.2 CH                                                                          H     H      O    n.sub.D.sup.21 : 1.5360                 A115 (CH.sub.3).sub.2 CH                                                                          H     H      S                                            A116 CH.sub.3 O(CH.sub.2).sub.2                                                                   H     H      O                                            A117                                                                                ##STR85##     H     H      O                                            A118                                                                                ##STR86##     H     H      O    n.sub.D.sup.21 : 1.5210                 A119                                                                                ##STR87##     H     CH.sub.3                                                                             O                                            A120                                                                                ##STR88##     H     CH.sub.3                                                                             O                                            A121 CH.sub.3 O(CH.sub.2).sub.2                                                                   H     CH.sub.3                                                                             O                                            A122 (CH.sub.3).sub.2 CH                                                                          H     CH.sub.3                                                                             O                                            A123                                                                                ##STR89##     H     CH.sub.3                                                                             O                                            A124                                                                                ##STR90##     H     CH.sub.3                                                                             SO.sub.2                                     A125                                                                                ##STR91##     H     CH.sub.3                                                                             S                                            A126                                                                                ##STR92##     H     CH.sub.3                                                                             O                                            ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                         ##STR93##                    (Iad)                                           No.  R.sup.1        Z     R.sup.11                                                                           R.sup.12                                                                           X    Phys. data                           ______________________________________                                        A127                                                                                ##STR94##     H     H    Cl   O                                         A128                                                                                ##STR95##     H     H    Cl   S                                         A129                                                                                ##STR96##     H     H    Cl   SO.sub.2                                  A130                                                                                ##STR97##     H     H    Cl   O                                         A131                                                                                ##STR98##     H     H    Cl   S                                         A132 (CH.sub.3).sub.2 CH                                                                          H     H    Cl   O                                         A133 CH.sub.3 O(CH.sub.2).sub.2                                                                   H     H    Cl   O                                         A134                                                                                ##STR99##     H     H    Cl   O                                         A135                                                                                ##STR100##    H     H    Cl   O                                         A136                                                                                ##STR101##    H     H    H    O                                         A137                                                                                ##STR102##    H     H    H    O                                         A138 CH.sub.3 O(CH.sub.2).sub.2                                                                   H     H    H    O                                         A139 (CH.sub.3).sub.2 CH                                                                          H     H    H    O                                         A140                                                                                ##STR103##    H     H    H    O                                         A141                                                                                ##STR104##    H     H    H    SO.sub.2                                  A142                                                                                ##STR105##    H     H    H    S                                         A143                                                                                ##STR106##    H     H    H    O                                         ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                         ##STR107##                   (Iae)                                           No.   R.sup.1       Z      R.sup.13                                                                           X     Phys. data                              ______________________________________                                        A144                                                                                 ##STR108##   H      H    O     n.sub.D.sup.25 : 1.5755                 A145                                                                                 ##STR109##   H      H    S                                             A146                                                                                 ##STR110##   H      H    SO.sub.2                                      A147                                                                                 ##STR111##   H      H    O                                             A148  (CH.sub.3).sub.2 CH                                                                         H      H    O     n.sub.D.sup.25 : 1.5817                 A149  CH.sub.3 O(CH.sub.2).sub.2                                                                  H      H    O                                             A150                                                                                 ##STR112##   H      H    O     n.sub.D.sup.25 : 1.5745                 A151                                                                                 ##STR113##   H      H    O                                             ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                         ##STR114##                   (Iaf)                                           No.  R.sup.1        Z     R.sup.3                                                                           R.sup.14                                                                            X    Phys. data                           ______________________________________                                        A152                                                                                ##STR115##    H     H   H     O                                         A153                                                                                ##STR116##    H     H   H     S                                         A154                                                                                ##STR117##    H     H   H     SO.sub.2                                  A155                                                                                ##STR118##    H     H   H     O                                         A156 (CH.sub.3).sub.2 CH                                                                          H     H   H     O                                         A157 CH.sub.3 O(CH.sub.2).sub.2                                                                   H     H   H     O                                         A158                                                                                ##STR119##    H     H   H     O                                         A159                                                                                ##STR120##    H     H   H     O                                         A160                                                                                ##STR121##    H     H   CH.sub.3                                                                            O                                         ______________________________________                                    

(B) Phenoxyalkyl-substituted heteroaromatics having a 5-membered ring(Q_(b)) 5-[4-(sec-Butoxy)-phenoxymethyl]-3-methylisoxazole (Ex. No. B1in the table below)

4.6 g of anhydrous potassium carbonate is added to 5.0 g of4-sec-butyloxyphenol in 80 ml of absolute dimethylformamide, and themixture is stirred for one hour at 80° C. At this temperature, 3.9 g of5-chloromethyl-3-methylisoxazole is dripped in and the mixture isstirred for a further seven hours at 90° C. The batch is then stirredinto 300 ml of ice water, extracted three times, each time with 100 mlof methyl tert-butyl ether and the organic phase is washed twice with 2Nsodium hydroxide solution (50 ml in each instance) and then three timeswith water (50 ml in each instance). Drying over sodium sulfate andremoval of the solvent under reduced pressure give 6.6 g of5-[4-(sec-butyloxy)-phenoxymethyl]-3-methylisoxazole, which is obtained,after chromatography over silica gel using toluene/ethyl acetate(1:1) aseluant, as a viscous oil. According to ¹ H-NMR spectroscopy, the oil ispure.

250 MHz ¹ H-NMR in CDCl₃ [ppm], (characteristic signals): 1.21 (d); 5.08(s); 6.15 (s).

5-[4-(sec-Butylthio)-phenoxymethyl]-3-cyclopropylisoxazole (Ex. No. B10in the table below)

Under a nitrogen blanket, 0.79 g of sodium hydride is added to 50 ml ofabsolute dimethylformamide. At room temperature, 5.5 g of4-sec-butylthiophenol dissolved in 20 ml absolute dimethylformamide isdripped in and the mixture is stirred for 30 minutes at 60° C. At thistemperature 5.8 g of 5-chloromethyl-3-cyclopropylisoxazole in 20 mlabsolute dimethylformamide is dripped in and, after all has been added,the mixture is stirred for 3 hours at 90° C. Working up as in the aboveexample gives, after chromatography over silica gel using toluene/ethylacetate (1:1) as eluant, 7.9 g of5-[4-(sec-butylthio)-phenoxymethyl]-3-cyclopropylisoxazole as a paleyellow oil.

250 MHz ¹ H-NMR in CDCl₃ [ppm]; (characteristic signals): 1.22 (d); 5.09(s); 6.01 (s).

2-[4-(sec-Butyloxy)-phenoxymethyl]-5-bromothiophene (Ex. No. B49 in thetable below)

6.64 g of 4-(sec-butyloxy)-phenol and 5.52 g of potassium carbonate areheated in 50 ml of anhydrous dimethylformamide for one hour at 70° C.Subsequently, 8.46 g of 5-bromo-2-chloromethylthiophene in 20 mlanhydrous dimethylformamide is dripped in. The mixture is stirred for 6hours at 80° C. and overnight at room temperature (about 20° C.). It isthen poured into 100 ml of ice water and extracted three times withethyl acetate, and the organic phases are dried over magnesium sulfate.The solvent is evaporated off to give a crude product which is purifiedby chromatography on silica gel using n-hexane/ethyl acetate (4:1) aseluant. There is obtained 6.3 g of2-[4-(sec-butyloxy)-phenoxymethyl]-5-bromothiophene as a colorless oil.

250 MHz ¹ H-NMR in CDCl₃ [ppm]; (characteristic signals): 0.99 (t); 1.28(d); 5.09 (s).

5-[4-(sec-Butyloxy)-phenoxymethyl]-3-cyclopropyl-1,2,4-oxadiazole (Ex.No. B69 in the table below)

5 g of 4-(sec-butyloxy)-phenol and 6.2 g of potassium carbonate arestirred in 50 ml of anhydrous dimethylformamide for 1 hour at 80° C.Subsequently, 4.8 g of 5-chloromethyl-3-cyclopropyl-1,2,4-oxadiazole in20 ml anhydrous dimethylformamide is dripped in and the mixture stirredfor 8 hours at 80° C. and overnight at room temperature (about 20° C.).The mixture is then poured into 100 ml of water and extracted threetimes with ethyl acetate, and the organic phases are dried overmagnesium sulfate. The solvent is evaporated off and the crude productis purified by chromatography on silica gel using n-hexane/ethyl acetate(4:1) as eluant. There is obtained 6.7 g of5-[4-(sec-butyloxy)-phenoxymethyl]-3-cyclopropyl-1,2,4-oxadiazole as acolorless oil.

250 MHz ¹ H-NMR in CDCl₃ [ppm]; (characteristic signals): 1.50-1.82 (m);2.04-2.18 (m); 5.13 (s).

                                      TABLE 7                                     __________________________________________________________________________     ##STR122##                                                                                                         Substitution                                                                  in position                                                                          250 MHz .sup.1 H-NMR [ppm]                                                    in CDCl.sub.3                    No. R.sup.1    R.sup.2                                                                           Z  X   Q.sub.b     . . . of Q.sub.b                                                                     (characteristic                  __________________________________________________________________________                                                 signals)                         B1                                                                                 ##STR123##                                                                              H   H  O                                                                                  ##STR124## 5      1.21 (d), 5.08 (s), 6.15                                                      (s)                              B2  (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2                                                     H   H  O                                                                                  ##STR125## 5      0.98 (d), 2.31 (s): 6.18                                                      (s)                              B3                                                                                 ##STR126##                                                                              H   H  O                                                                                  ##STR127## 5      0.92 (t), 1.26 (d), 5.09                                                      (s)                              B4                                                                                 ##STR128##                                                                              H   H  O                                                                                  ##STR129## 5      0.93 (t), 1.22 (d), 2.31                                                      (s)                              B5                                                                                 ##STR130##                                                                              H   H  O                                                                                  ##STR131## 5      2.28 (s), 5.08 (s), 6.17                                                      (s)                              B6                                                                                 ##STR132##                                                                              H   H  S                                                                                  ##STR133## 5      2.30 (s), 5.12 (s), 6.19                                                      (s)                              B7  (CH.sub.3).sub.2 CH                                                                      H   H  O                                                                                  ##STR134## 5      1.31 (d), 2.33 (s), 6.19                                                      (s)                              B8  (CH.sub.3).sub.3 CCH.sub.2 CH.sub.2                                                      H   H  O                                                                                  ##STR135## 5      0.98 (s), 2.31 (s), 5.10                                                      (s)                              B9                                                                                 ##STR136##                                                                              H   H  O                                                                                  ##STR137## 5      1.22 (d), 5.10 (s), 5.98                                                      (s)                              B10                                                                                ##STR138##                                                                              H   H  S                                                                                  ##STR139## 5      1.22 (d), 5.09 (s), 6.01                                                      (s)                              B11                                                                                ##STR140##                                                                              H   H  SO.sub.2                                                                           ##STR141## 5      1.05 (t), 5.22 (s), 6.09                                                      (s)                              B12                                                                                ##STR142##                                                                              H   H  O                                                                                  ##STR143## 5      1.32 (d), 4.21-4.83 (m),                                                      5.02 (s)                         B13 (CH.sub.3).sub.2 CH                                                                      H   H  O                                                                                  ##STR144## 5      1.35 (d), 5.08 (s), 6.89                                                      (s)                              B14                                                                                ##STR145##                                                                              H   H  O                                                                                  ##STR146## 5      1.28 (d), 3.46 (s), 5.98                                                      (s)                              B15 CH.sub.3 OCH.sub.2 CH.sub.2                                                              H   H  O                                                                                  ##STR147## 5      3.42 (s), 3.63-3.71 (m),                                                      3.91-4.05 (m)                    B16                                                                                ##STR148##                                                                              H   H  O                                                                                  ##STR149## 5      4.08 (d), 5.05 (s), 6.00                                                      (s)                              B17                                                                                ##STR150##                                                                              H   H  O                                                                                  ##STR151## 5      1.23 (d), 4.98 (s), 5.96                                                      (s)                              B18                                                                                ##STR152##                                                                              H   H  O                                                                                  ##STR153## 5                                       B19                                                                                ##STR154##                                                                              H   H  O                                                                                  ##STR155## 5      3.48 (s), 5.07 (s), 6.00                                                      (s)                              B20                                                                                ##STR156##                                                                              H   H  O                                                                                  ##STR157## 5                                       B21                                                                                ##STR158##                                                                              H   H  S                                                                                  ##STR159## 5                                       B22 CH.sub.3 OCH.sub.2 CH.sub.2                                                              H   H  S                                                                                  ##STR160## 5                                       B23                                                                                ##STR161##                                                                              H   H  S                                                                                  ##STR162## 5                                       B24 C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2                                                       H   H  O                                                                                  ##STR163## 5                                       B25                                                                                ##STR164##                                                                              H   H  O                                                                                  ##STR165## 3                                       B26                                                                                ##STR166##                                                                              H   H  S                                                                                  ##STR167## 3                                       B27                                                                                ##STR168##                                                                              H   H  SO.sub.2                                                                           ##STR169## 3                                       B28 (CH.sub.3).sub.2 CH                                                                      H   H  O                                                                                  ##STR170## 3                                       A29                                                                                ##STR171##                                                                              H   H  O                                                                                  ##STR172## 3      1.27 (d), 3.40 (s), 5.18                                                      (s)                              A30 CH.sub.3 OCH.sub.2 CH.sub.2                                                              H   H  O                                                                                  ##STR173## 3                                       A31                                                                                ##STR174##                                                                              H   H  O                                                                                  ##STR175## 3                                       A32                                                                                ##STR176##                                                                              H   H  O                                                                                  ##STR177## 3                                       A33                                                                                ##STR178##                                                                              H   H  O                                                                                  ##STR179## 2      0.98 (t), 1.50-1.82 (m),                                                      2.11-2.24 (m)                    A34                                                                                ##STR180##                                                                              H   H  S                                                                                  ##STR181## 2                                       A35                                                                                ##STR182##                                                                              H   H  SO.sub.2                                                                           ##STR183## 2                                       B36                                                                                ##STR184##                                                                              H   H  O                                                                                  ##STR185## 2                                       B37 (CH.sub.3).sub.2 CH                                                                      H   H  O                                                                                  ##STR186## 2                                       B38 CH.sub.3 OCH.sub.2 CH.sub.2                                                              H   H  O                                                                                  ##STR187## 2                                       B39                                                                                ##STR188##                                                                              H   H  O                                                                                  ##STR189## 2                                       B40                                                                                ##STR190##                                                                              H   H  O                                                                                  ##STR191## 2                                       B41                                                                                ##STR192##                                                                              H   H  O                                                                                  ##STR193## 5      1.27 (d), 1.50 (t), 5.24                                                      (s)                              B42                                                                                ##STR194##                                                                              H   H  S                                                                                  ##STR195## 5      1.20 (d), 1.47 (t), 5.28                                                      (s)                              B43                                                                                ##STR196##                                                                              H   H  SO.sub.2                                                                           ##STR197## 5                                       B44                                                                                ##STR198##                                                                              H   H  O                                                                                  ##STR199## 5      1.24 (d), 1.32 (t), 5.25                                                      (s)                              B45 (CH.sub.3).sub.2 CH                                                                      H   H  O                                                                                  ##STR200## 5      1.29 (d), 1.45 (t), 5.24                                                      (s)                              B46                                                                                ##STR201##                                                                              H   H  O                                                                                  ##STR202## 5      1.48 (t), 2.03-2.19 (m),                                                      5.33 (s)                         B47                                                                                ##STR203##                                                                              H   H  O                                                                                  ##STR204## 5      1.26 (d), 1.47 (t), 5.25                                                      (s)                              B48 CH.sub.3 OCH.sub.2 CH.sub.2                                                              H   H  O                                                                                  ##STR205## 5      1.46 (t), 3.47 (s), 5.28                                                      (s)                              B49                                                                                ##STR206##                                                                              H   H  O                                                                                  ##STR207## 5      0.99 (t), 1.28 (d), 5.09                                                      (s)                              B50                                                                                ##STR208##                                                                              H   H  S                                                                                  ##STR209## 5      1.22 (d), 1.37-1.58 (m),                                                      6.71-6.96 (m)                    B51                                                                                ##STR210##                                                                              H   H  SO.sub.2                                                                           ##STR211## 5                                       B52                                                                                ##STR212##                                                                              H   H  O                                                                                  ##STR213## 5      1.63-1.91 (m), 4.23-4.38                                                      (m), 5.02 (s)                    B53 (CH.sub.3).sub.2 CH                                                                      H   H  O                                                                                  ##STR214## 5      4.45-4.52 (m), 5.08 (s),                                                      6.71-6.92 (m)                    B54 CH.sub.3 OCH.sub.2 CH.sub.2                                                              H   H  O                                                                                  ##STR215## 5      3.47 (s), 3.70-3.78 (m),                                                      4.02-4.10 (m)                    B55                                                                                ##STR216##                                                                              H   H  O                                                                                  ##STR217## 5      1.26 (d), 3.39 (s), 5.04                                                      (s)                              B56                                                                                ##STR218##                                                                              H   H  O                                                                                  ##STR219## 5      1.37 (t), 2.05-2.17 (m),                                                      4.07 (d)                         B57                                                                                ##STR220##                                                                              H   H  O                                                                                  ##STR221## 5                                       B58                                                                                ##STR222##                                                                              H   H  S                                                                                  ##STR223## 5                                       B59                                                                                ##STR224##                                                                              H   H  O                                                                                  ##STR225## 3      1.24 (d), 3.85 (s), 4.91                                                      (s)                              B60                                                                                ##STR226##                                                                              H   H  S                                                                                  ##STR227## 3      3.83 (s), 4.92 (s), 5.94                                                      (s)                              B61                                                                                ##STR228##                                                                              H   H  SO.sub.2                                                                           ##STR229## 3                                       B62                                                                                ##STR230##                                                                              H   H  O                                                                                  ##STR231## 3      1.22 (d), 3.87 (s), 4.92                                                      (s)                              B63                                                                                ##STR232##                                                                              H   H  O                                                                                  ##STR233## 3      2.03-2.19 (m), 4.93 (s),                                                      5.95 (s)                         B64 CH.sub.3 OCH.sub.2 CH.sub.2                                                              H   H  O                                                                                  ##STR234## 3      3.43 (s), 4.93 (s), 5.93                                                      (s)                              B65                                                                                ##STR235##                                                                              H   H  O                                                                                  ##STR236## 3      1.28 (d), 3.89 (s), 5.94                                                      (s)                              B66 (CH.sub.3).sub.2 CH                                                                      H   H  O                                                                                  ##STR237## 3      1.29 (d), 4.92 (s), 5.93                                                      (s)                              B67                                                                                ##STR238##                                                                              H   H  O                                                                                  ##STR239## 4                                       B68                                                                                ##STR240##                                                                              H   H  O                                                                                  ##STR241## 4                                       B69                                                                                ##STR242##                                                                              H   H  O                                                                                  ##STR243## 5      1.50-1.82 (m), 2.04-2.18                                                      (m), 5.13 (s)                    B70                                                                                ##STR244##                                                                              H   H  S                                                                                  ##STR245## 5                                       B71                                                                                ##STR246##                                                                              H   H  O                                                                                  ##STR247## 5                                       B72                                                                                ##STR248##                                                                              H   H  O                                                                                  ##STR249## 5                                       B73                                                                                ##STR250##                                                                              H   H  O                                                                                  ##STR251## 4      1.52-1.84 (m), 4.93 (s),                                                      7.08 (s)                         B74                                                                                ##STR252##                                                                              H   H  O                                                                                  ##STR253## 2      0.98 (t), 1.51-1.82 (m),                                                      2.28 (s)                         B75                                                                                ##STR254##                                                                              H   H  O                                                                                  ##STR255## 2      5.10 (s), 6.72-7.06 (m),                                                      7.28-7.32 (m)                    B76                                                                                ##STR256##                                                                              H   H  O                                                                                  ##STR257## 3      4.12-4.28 (m), 5.05 (s),                                                      7.30-7.41 (m)                    B77                                                                                ##STR258##                                                                              H   H  O                                                                                  ##STR259## 4      4.01-4.24 (m), 4.88 (s),                                                      7.32 (s)                         B78                                                                                ##STR260##                                                                              H   H  O                                                                                  ##STR261## 4      1.48-1.82 (m), 6.75-6.98                                                      (m), 7.18 (s)                    B79                                                                                ##STR262##                                                                              H   H  O                                                                                  ##STR263## 2      1.23 (d), 2.52 (s), 5.12                                                      (s)                              B80                                                                                ##STR264##                                                                              H   H  O                                                                                  ##STR265## 4                                       B81                                                                                ##STR266##                                                                              H   H  S                                                                                  ##STR267## 4                                       B82                                                                                ##STR268##                                                                              H   H  O                                                                                  ##STR269## 4                                       B83                                                                                ##STR270##                                                                              H   H  O                                                                                  ##STR271## 4                                       B84 CH.sub.3 OCH.sub.2 CH.sub.2                                                              H   H  O                                                                                  ##STR272## 4                                       B85                                                                                ##STR273##                                                                              CH.sub.3                                                                          H  O                                                                                  ##STR274## 5                                       B86                                                                                ##STR275##                                                                              H   2-F                                                                              O                                                                                  ##STR276## 5                                       B87                                                                                ##STR277##                                                                              H   2-F                                                                              O                                                                                  ##STR278## 5                                       B88                                                                                ##STR279##                                                                              H   H  O                                                                                  ##STR280## 2      1.26 (d), 2.32-2.47 (m),                                                      5.39 (s)                         B89                                                                                ##STR281##                                                                              H   H  S                                                                                  ##STR282## 2      1.20 (d), 2.32-2.65 (m),                                                      5.42 (s)                         B90                                                                                ##STR283##                                                                              H   H  SO.sub.2                                                                           ##STR284## 2                                       B91                                                                                ##STR285##                                                                              H   H  O                                                                                  ##STR286## 2      1.23 (d), 2.32-2.66 (m),                                                      5.38 (s)                         B92                                                                                ##STR287##                                                                              H   H  O                                                                                  ##STR288## 2      2.01-2.19 (m), 2.32-2.47                                                      (m), 5.39 (s)                    B93 CH.sub.3 OCH.sub.2 CH.sub.2                                                              H   H  O                                                                                  ##STR289## 2      2.28- 2.48 (m), 3.43 (s),                                                     5.34 (s)                         B94                                                                                ##STR290##                                                                              H   H  O                                                                                  ##STR291## 2      1.28 (d), 2.34-2.48 (m),                                                      5.40 (s)                         B95 (CH.sub.3).sub.2 CH                                                                      H   H  O                                                                                  ##STR292## 2      1.30 (d), 2.31-2.48 (m),                                                      5.38 (s)                         B96                                                                                ##STR293##                                                                              H   H  O                                                                                  ##STR294## 2      2.32-2.47 (m), 3.98-4.12                                                      (m), 5.35 (s)                    __________________________________________________________________________

USE EXAMPLES FOR N-PHENOXYMETHYL-SUBSTITUTED AZOLES Ia

In the examples that follow, the action of compounds according to theinvention, or agents containing them, on pests was compared with that ofthe following prior art compounds. The purity of the substances and ofthe comparative agents was in excess of 95%.

    __________________________________________________________________________    A:                                                                               ##STR295##              disclosed in EP 132,606 as compound no. 1          B:                                                                               ##STR296##              disclosed in EP 132,606 as compound no. 8          C:                                                                               ##STR297##              disclosed in EP 132,606 as compound no.            __________________________________________________________________________                               29                                             

The concentrations at which the candidate compounds exhibit 100% kill orinhibition are the minimum concentrations. At least two experiments wererun for each concentration and an average was formed.

EXAMPLE A.a Dysdercus intermedius (Cotton Stainer), Ovicidal Action

Pieces of adhesive tape (about 0.8 cm) were stuck to the top edge ofplastic plant markers. 24 hours before commencement of the experiment,eggs of the cotton stainer contained in a vessel were attached to theadhesive strips by dipping the markers into the vessel.

The eggs were then dipped for 5 seconds into aqueous formulations of theactive ingredients and excess liquid was allowed to drip off onto filterpaper, care being taken to prevent the eggs coming into contact with thepaper.

The markers were placed (adhesive tape up) in plastic pallets. Half aroll of absorbent cotton was moistened with water and placed in eachbeaker to prevent drying out, and the pallets were covered with a glassplate.

Assessment took place after about 8 days (after the larvae in thecontrol batch had hatched). Hatch inhibition was assessed in %.

In this experiment, the compounds of Examples A1, A4, A20, A42 and A60achieved 80% hatch inhibition at concentrations of 100 ppm and less,whereas comparative agents A, B and C did not inhibit hatching at aconcentration of 1,000 ppm.

EXAMPLE B.a Dysdercus intermedius (Cotton Stainer); Breeding Experiment

Petri dishes 10 cm in diameter were lined with 1 ml of acetonicsolutions of the active ingredients. After the solvent had evaporated,20 larvae of the penultimate stage were placed in each dish.

After 24 hours, the surviving animals were transferred to 1 liter jarscontaining 200 g of sterile sand (particle size: 0 to 3 mm). Prior tothe experiment, 25 ml of aqueous active ingredient formulations werepoured onto this sand.

The food proffered was swollen cotton seeds, which were changed weekly.The sand was moistened with pure water--again once a week.

The temperature was kept at 25° to 27° C. The jars were monitored untilthe eggs in the control batch hatched.

In this experiment, the compounds of Examples A1, A4, A5, A20, A42 andA60 achieved a kill rate of 100% at a concentration of 10 ppm and less,whereas the comparative agents were virtually ineffective at aconcentration of 25 ppm, i.e., achieved a kill rate of less than 60%.

USE EXAMPLES FOR PHENOXYALKYL-SUBSTITUTED HETEROAROMATICS BEARING A5-MEMBERED RING

In the examples that follow, the action of compounds according to theinvention, or agents containing them, on pests was compared with that ofthe following prior art compounds:

    __________________________________________________________________________       ##STR298##                 disclosed in DE-A 25 16 331                     E                                                                                ##STR299##                 disclosed in EP-A 239 047                       __________________________________________________________________________

The purity of the comparative agents and of the compounds according tothe invention was at least 90 to 95%. The concentrations at which thecandidate compounds exhibit 100% kill or inhibition are the minimumconcentrations. At least two experiments were run for eachconcentration.

Dysdercus intermedius (Cotton Stainer), Ovicidal Action

Pieces of adhesive tape (about 0.8 cm) were stuck to the top edge ofplastic plant markers. 24 hours before commencement of the experiment,eggs of the cotton stainer contained in a vessel were attached to theadhesive strips by dipping the markers into the vessel.

The eggs were then dipped for 5 seconds into aqueous formulations of theactive ingredients and excess liquid was allowed to drip off onto filterpaper, care being taken to prevent the eggs coming into contact with thepaper.

The markers were placed (adhesive tape up) in plastic pallets. Half aroll of absorbent cotton was moistened with water and placed in eachbeaker to prevent drying out, and the pallets were covered with a glassplate.

Assessment took place after about 8 days (after the larvae in thecontrol batch had hatched). Hatch inhibition was assessed in %.

In this experiment, compounds B1, B4 and B7 achieved 80% hatchinhibition at concentrations of 400 ppm and less, whereas comparativeagent D did not inhibit hatching at a concentration of 1,000 ppm.

EXAMPLE B.b Caenorhabditis elegans (Nematodes); Contact Experiment

0.5 ml of acetonic solutions of the active ingredients was applied tothe surface of a nutrient medium (5 ml in plastic Petri dishes 35 mm indiameter and 10 mm high). After the acetone had evaporated, the mediumwas infected with 30 μl of E-coli bacteria and 50 μl of nematodesuspension. After 48 hours, the contact action was assessed in % kill.

At an active ingredient concentration of 100 ppm, the compounds ofExamples B2, B3, B4, B5 and B49 achieved a kill rate of 100%, whereascomparative agents D and E were virtually ineffective at thisconcentration, i.e., achieved a kill of less than 60%.

We claim:
 1. Phenoxyalkyl-substituted heteroaromatics of the formula Ia ##STR300## where the substituents have the following meanings: R¹ C₁ -C₁₂ -alkyl, C₂ -C₁₂ -alkenyl, C₂ -C₁₂ -alkynyl, C₁ -C₁₂ -haloalkyl, C₂ -C₁₂ -haloalkenyl, C₂ -C₁₂ -haloalkynyl, C₃ -C₁₂ -alkoxyalkyl, C₃ -C₈ -cycloalkyl, C₄ -C₁₂ -cycloalkylalkyl, C₃ -C₈ -halocycloalkyl, C₄ -C₁₂ -halocycloalkylalkyl, C₄ -C₁₂ -cycloalkylhaloalkyl or C₄ -C₁₂ -halocycloalkylhaloalkyl;X O, S, SO₂ ; Z hydrogen, halogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, C₃ -C₁₀ -cycloalkyl, nitro or cyano; Q_(a) unsubstituted or substituted azole radical of the formula IIa or IIb ##STR301## where R³ is hydrogen, and R⁴ to R⁸ are hydrogen, halogen, C₁ -C₈ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₃ -C₁₀ -cycloalkyl or aryl which is unsubstituted or mono- to trisubstituted by halogen, C₁ -C₈ -alkoxy, C₁ -C₄ -haloalkyl or C₁ -C₄ -haloalkoxy.
 2. An agent for combating insects, mites and nematodes containing a phenoxyalkyl-substituted heteroaromatic of the formula Ia as set forth in claim 1, and conventional carriers.
 3. An agent for combating insects, mites and nematodes as set forth in claim 2, containing from 0.1 to 95 wt % of a phenoxyalkyl-substituted heteroaromatic of the formula I as set forth in claim
 1. 4. A process for combating insects, mites and nematodes, wherein an insecticidally, miticidally and nematodicidally effective amount of a phenoxyalkyl-substituted heteroaromatic of the formula Ia as set forth in claim 1 is allowed to act on insects, mites and nematodes or their habitat.
 5. The phenoxyalkyl-substituted heteroaromatic of formula Ia as set forth in claim 1, wherein R¹ is C₁ -C₁₂ alkyl, X is 0 or S, Z is hydrogen, and Q_(a) is (IIa).
 6. The phenoxyalkyl-substituted heteroaromatic of formula Ia as set forth in claim 5 wherein Q_(a) is (IIa) with R³ being hydrogen and R⁴ and R⁵ being chloro.
 7. The phenoxyalkyl-substituted heteroaromatic of formula Ia as set forth in claim 5 wherein R¹ is branched C₁ -C₁₂ alkyl.
 8. The phenoxyalkyl-substituted heteroaromatic of formula Ia as set forth in claim 7 wherein R¹ is secbutyl.
 9. The phenoxyalkyl-substituted heteroaromatic of formula Ia as set forth in claim 5 wherein X is
 0. 